反应详情

A solution of 2-hydroxyimino-2-(1-naphthyl)acetonitrile (7.0 g.) and dimethylaniline (12.0 g.) in toluene (100 ml.) was added dropwise, under ice-cooling, to a solution of trichloromethyl chloroformate (phosgene dimer) (3.56 g.) in benzene (30 ml.). The mixture was stirred for 3 hours at the same temperature and allowed to stand overnight. A solution of tert-butyl alcohol (11.1 g.) and pyridine (12 ml.) in toluene (20 ml.) was added dropwise, under ice-cooling, to the resultant mixture containing 2-chlorocarbonyloxyimino-2-(1-naphthyl)acetonitrile. The mixture was stirred for 6 hours at the same temperature and allowed to stand overnight. The reaction mixture was then washed with water, 1 N hydrochloric acid, water, a sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate. The solution was concentrated under reduced pressure and n-hexane and methanol were added to the residue. The mixture was allowed to stand in a refrigerator and the precipitated crystals were collected by filtration and recrystallized twice from methanol to give 2-tert-butoxycarbonyloxyimino-2-(1-naphthyl)acetonitrile (3.3 g.), mp 90° to 92° C.

1. waitto stand overnight
2. stirringThe mixture was stirred for 6 hours at the same temperature
3. waitto stand overnight
4. washThe reaction mixture was then washed with water, 1 N hydrochloric acid, water
5. dry with materiala sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate
6. concentrationThe solution was concentrated under reduced pressure and n-hexane and methanol
7. additionwere added to the residue
8. filtrationthe precipitated crystals were collected by filtration
9. customrecrystallized twice from methanol